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- April 6, l

EU 6') VEEING F:

Hall 35 1013133)? G ll/CHRIST, OF NEW Be it known ihol; l, EDWARD d HASLUP, a citizenof the United States, residing el;

New York city, in the county of l lew llorlr and. State of New York, have i1 ed certain new and useful lniproveuiems in. lProcesses of Recovering Fixed Nitrogen; and l: do hereby declare he follmvii to be :2 full, clear, and exact description oi die inveneion, such us will enable others skilled in the to which it apperiains lo make and use the same.

This invention relates to a, 'gjn'ocess for effooting the fixation of etnwspheric nitrogen as a byproduct in ine-nufactiuiug producer gas, and has for its object we provide method which will be'iiuore exjoe llilflus and less costly than, has hereofcre been proposed, I

With this and other, chic in View the invention consists in Llie novel steps and combinations of steps ooi'isiitu-tiug the proc ess, ell as will more fully h reinafter l1sclosed and particularly point d col; in the claims. I e

In order thee; the pre ise neiure oi the or went-ion inuy be more cieeriy understood 1i) is said I .ltis uown um when free or com loined alkuii cities or alka i cart metal oxide cepelile of feminine; selts'with acids ere exposed ic carbon and heated to suiiicien'tly high temperate in on atmosphere of nitrogen freeof oriidizing such as oxygen, carlion dicxid, old, that nit]? zen carlvcn con. ining compound is forined, which ct its is of :llormeiion volatile, or at least has the physicel"prop erties of a sublimete.

Processes u tiliaing ill is principle have been made "(he subjec' of .1 scents :gbldllsill; #133 32.-

glfrldfie; 13; each dated Peecoclit.

lo, end issued to Samuel But in. following the proceduie of s'eid pebents, ii: is tool; only to lfil'lTlDVG the subliined nitrogenous compound or carbonitrid from a furnace chamber necz. erily sealed from the air, to prevent do oyiug the compound, but the car l'iocii values music he colleclcd and cooled c1 contact with ihe air, by some menus, and in such a iemperature as will. precludetheir i, 7i')illpO- Specification oi Patented July 22, 319%).

fwplieaiion filed npril #3, 1912;. Eerie No $327,316.

sieion upon contact with oxygen, and all in a continuous industrial operation.

Ti lie mechanical problem thus presented in ceriying one an industrial procedure is evidenlily a, very difiiculi; one In practice all processes of this kind for such nitrogen fixei ion have been limited in their operation to the use of electrically generated heat, in one form or another, for electricity seemed '00 fuz' nish the only means of readily obtaining the desired temyieraturein a sealed fur- But electrically genera-ted heat is comparatively costly. In fact, the heat equive-len" of a kilowatt year which may cost from say 2825 to $100 is found in less then three thousand pounds of ordinary steam coal. is true that there sue a few localities where hydro-electric power may be obtained at a cost. of approximately $15 per kilowatt year; but, it is also true that there are a greater number of locations Where 8000 pounds of coal would ost from sayvthree to four dollars only. Hence, it obvious that a procedure which enable the use of directly generated heat from coal in such nitrogen fixation processes would be an economic gain. New, 1t is' Well known, in the operation of e carbon monoxid gas producer, or in the operation of a blast furnace "that if one examines the furnace or twyers, he will find the furnace gases to contain neither free oxygen, carbon dioxid, nor other readily oxidizing gases, and that the gaseous nitrogen present; ranges from say "no 66 per cent. of the total volume. iihelempemture of the furnace gases at this pointalso, will oe foundito be very. high, nly alcove 1060" C, while the temperainure oi? the coke and inorganic bodies in this zone of high temperature exceeds say 14l0O C, In ordinary blast furnace, at such lemperaiures, "most oxide in contact with carbon and in the presence of gaseous nisrogen, form a, nitrogen containing compound, or cairbo-nitricl, which has approximately the proportional formula RCN and which when hearted with water produces ammonia. But, unless prevented, these com-- contact with the air, producing a white cloud of fume consisting of oxids and carbonates of, the combined metals present in a state of very fine sub-division. If an iron blast furnace is used, the action of the carbon monoxid of the furnace gases upon the iron oxid present results in the formation of metallic iron and carbon dioxid, and

limate or carbo-nitrid, is more or less condensed by the cold charge at the furnace top, and iscarried down with the descending charge until it reaches a temperature high enough to combine with the silicious slag making material of the furnace charge but not high enough to cause the nitrogen compound to'sublime. As a result, a silicate of the carbo-nitrid metal is formed with the evolution of free nitrogen.

It does not seem to have occurred to any one prior to my invention that if the furnace gases be removed from an exit located so low in the furnace that no substantial condensation of said carbo-nitrids will occur, and too low for the usual reducing effect to take place, that said carbo-nitrids could be tapped out and recovered. The reason why no one seems to have suggested such a procedure, probably resides in the fact that the tapping of the furnace gases in any such fashion from an iron blast furnace would render the latter inoperative; and the tapping of the furnacegases in such manner from a producer gas furnace would be a useless procedure, for no earbo-nitrids would be present.

One the other hand, were not these two objections present, it would be perfectly feasible to employ either a blast furnace, or a producer furnace in the manner stated, and to obtain carbo-nitrids of the character disclosed in the patents above referred to.

In carrying out this invention, I avoid the foregoing objections and obtain carbonitrids from either a blast or a producer type of furnace by proceeding as follows I charge the furnace with feldspar and coke, or lime and coke, or magnesia and coke, or other oXid (capable of forming a salt with an acid) and coke, precisely as an iron blast furnace, or gas producer is charged, and I make producer gas, usinga hot blast. In some cases, suitable fluxes may also be added to the charge, for the purpose of conveniently removing such materials as silica from the-furnace as a molten slag. I prefer, however, to finely grind the coke'and the oXid containing salt or mineral,

and briquet the same for furnace treatment. The following four chemical equations, stated in proportional formulas, illustrate the substantial reactions that take place In all four of these illustrations, the re action involves a high temperature zone of not less than say MOO C. If this temperature is raised to 1600O. the alumina of the feldspar is also converted to the nitrogen compound. I

In carrying out the access the use of a hot blast is very desirable in most cases, in order to keep the charge sufficiently molten to secure a readily flowing slag. As no iron oxids are to be reduced no objection is encountered in tapping oil the furnace gases at a suitable point near the twyers, or where the carbo'nitrids are found to be richest, and this I do. Ordinarily such a point in a blast furnace is found to be at the usual reducing zone. After the furnace gases have been thus led from. the reducing zone, they are carried out of contact with the air to any suitable scrubber, or collector, where the carbo nitrids contained therein are cooled down to a point where contact will the air does not affect them, and recovered without substantial loss.

It will now be clear that by making producer gas in a regular producer gas furnace, or in an iron blast type of furnace, and by having present in such furnaces a material containing an oxid of an alkali metal, or of an alkali-earth metal, during the process of making saidproducer gas, I am enabled to not only fix atmospheric nitrogen as a byproduct, without the use of electric heat, but I am enabled to continuously'ta it directly from the reducing zones of said furnaces and thus avoid its condensation on the cooler portions ofsaid furnaces, and on their charge material; I am also enabled to cool said carbonitrids without exposure to the air; results that have not been heretofore attained in so faras I am aware.

The reaction velocities are of courseincases to the successful operation of the process. The gas which finally exits from the settlers or scrubbers is found to be a high grade producer gas suitable for use in internal combustion engines.

What I claim is:

1.. The process of producing a volatile carbo-nitrid which consists in'preparing a mixture of an oXid bearing material and carbon; subjecting said mixturein a fuel fed furnace and in an atmosphere of producer gas to a temperature suificient to produce said carbo-nitrid; tapping out said carbo-nitrid and said producer gas-from a region of said furnace too 4 nace ata temperatureand under conditions suitable for forming "a, mixture of producer gas and a volatile carbo-nitrid; tapping off said mixture out of contact'with the air from a point in said furnace at which the temperature is sufiicient to prevent the condensation of said carbo-nitrid; and recovering the latter, substantially as described.

3. The process of fixing atmospheric nitrogen which consists in preparing a mixture of carbon and a material containing an oxid capable of forming a salt with an acid; heating said mixture under conditions suitable for forming a second mixture of carbon monoxid gas and a volatile carbo-nitrid;

leading off said mixture out of contact with "the air before sa1d carbo-nitrid has condensed; and recovering the latter, substantially as described. a

4. The process of fixing atmospheric nitrogen in a fuel fed furnace which consists in charging said furnace with a mixture containing calcium oXid and carbon; heating said mixture under conditions suitable for formin producer gas and a volatile carbo-nitri tapping said furnace at a point the temperature of which is too high to permit the condensation of said carbo-nitrid;

and cooling the latter out of contact with the air substantiall as described.

.'5. The process making and recovering volatile carbo-nitrids which consists in producing said carbo-nitrids in an atmosphere of carbon monoxid gas in a fuel fed furn'ace; and withdrawing said carbo-nitrids before condensation along with a ortion of said carbon monoxid gas, substantially as described. p

In testimony whereof I afiix my signature, in presence of two Witnesses.

EDWARD W. HASLUP.

Witnesses:

M. O. WALSH, M. M. MURPHY DREW. 

